Green dye and process of making same.



NITED TATES ATENT FFICE.

JOSEPI-I KOETSCHET, OF ST. FONS, NEAR LYONS, FRANCE, ASSIGNOR TO SO-CIETE CHIlWIIQUE DES USINES DU RHONE, ANCIENNEMENT GILLIARD, P. MONNETET CARTIER, OF LYONS, FRANCE, A CORPORATION OF FRANCE.

GREEN DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 709,160, datedSeptember 16, 1902.

Application filed June 18,I 1901. fierial No. 65,050. (No specimens) TottZZ whom it may concern.-

Be it known that I, JOSEPH KOETSCHET, chemist at the works ofSocitChimiquedes Usines du Rhone, anciennement Gilliard, P.

Monnet et Cartier, of St. Fons, near Lyons, France, have inventedcertain new and useful Improvements in the Manufacture ofColoring-Matters from Sulfonated Aldehydes, of which the following is as ecification.

IO The presentinvention relates to the manufacture of coloring-mattersfrom ortho-sulfonated derivatives of toluylic aldehyde.

When benzoic aldehyde is treated with sulfuric acid, it is transformedsubstantially into the meta-sulfonic acid of benzoic aldehyde, and ithas been impossible to manufacture by direct sulfonation the orthoderivative, which possesses very valuable properties, particularly theproperty of yielding 2o coloring-matters very fast to alkalies oncondensation with aromatic amins.

I have, as described in another application for patent by menamely,Serial No. 65,049, filed June 18, l90l--discovered that meta- 2 5toluylic aldehyde behaves toward sulfonating agents diiferently tobenzoic aldehyde and that ortho-sulfonated derivatives of meta toluylicaldehyde may be readily obtained by direct sulfonation. I have furtherdiscovered that the sulfonated meta-toluylic aldehyde thus obtainedpossesses analogous properties to ortho-sulfo-benzoic aldehyde, notablyin yielding with aromatic amins-such, for example, as dimethyl anilin,diethyl anilin, and

ethyl-benzyl-anilin, methyl-toluidin, ethyl toluidin, or theirsubstitution derivativessuch, for example, as ethyl-benzyl-anilinsulfonic acid, dibenzyl sulfonic acid, toluidin para-sulfonic acid, andnaphtylamin sulfonic acid, the leuco bases of bluish-greencoloringmatters of great value, being dyestuffs fast to alkalies.

The sulfonation of meta toluylic aldehyde to produce the sulfonatedaldehyde, which it is intended to condense with aromatic amins to formcoloring-matters of the kind above referred to, may conveniently becarried out according to the following example, in which sulfuric acidcontaining sixty per cent. anhydrid is employed as sulfonating agent ata low temperature, under which conditions the ortho-mono-sulfonic acidis the main product.

It will, however, be understood that any other suitable means ofsulfonating may be employed and that the temperature and otherconditions mentioned in the example may be varied.

Example of the preparation of sulfonaied metatolttyl aZdeh L (Ze.Onepart, by weight, of meta toluylic aldehyde is run slowly into ten parts,by weight, of sulfuric acid containing sixty per cent. anhydridpreviously cooled to 0 centigrade. The temperature of the mixture ismaintained between 0 Centigrade and 5 ceutigrade during the mixing, andthe mixture is then allowed to stand several hours to allow the reactionto be completed, the temperature finally rising to about 20 or 25centigrade, or the temperature may be kept between 0 and 5 centigradeuntil the complete solubility of a test in water shows the reaction tobe completed. The product of the reaction is then poured upon ice, whenan aqueous solution is obtained. The excess of sulfuric acid may beremoved and the sulfonated meta toluylic aldehyde obtained in the formof its barium salt by neutralization of the solution with carbonate ofbariu ml. After filtering off the barium sulfate formed by the excess ofsulfuric acid the barium salt of the sulfonated meta-toluyl aldehyde maybe isolated by evaporation of the filtrate and purified byrecrystallization of the barium salt, which is a White powder easilysoluble in hot water, less soluble in cold water, and crystallizes inneedles. The solution of this salt gives with phenyl hyd razin aprecipitate characteristic of aldehydes. From the barium salt othersalts or free sulfonic acid may be prepared. 0

I do not in the present application for patent make any claim to theproduction of sulfonated meta-toluylic aldehyde, as this forms thesubject of the separate application for patent hereinbefore mentioned. 5

According to the present invention I condense the new snlfonatedmeta-toluylic aldehyde above referred to with aromatic amins or theirsulfo-acids in the proportion of one molecule of the aldehyde to twomolecules of mo the amin or sulfo-acid, or it may be one molecule of thealdehyde to one molecule each of an aromatic amin and a sulfo-acid of anaromatic amin, and I thus obtain the leuco bases of valuble newcoloring-matters of bluish-green shades fast to alkali. Thesecoloring-matters possess the composition O H (SO H)COH( )2 X indicatingan aromatic amin radical. As examples of the aromatic amins which can beso condensed with the new sulfonated aldehyde are dimethyl anilin,diethyl anilin, ethyl benzyl anilin,

methyl-toluidin,ethyl-toluidin, and theirsubstitution derivatives-such,for example, as ethyl-benzyl-anilin sulfonic acid, dibenzyl sulfonicacid, toluidin-p-sulfonic acid, naphtylamin sulfonic acid.

In order to effect the condensation of the new sulfonated toluylicaldehyde with the aromatic amin, any ordinary method may be followedwhich is usually employed in condensing similar compounds; but I willproceed to give the following examples of the condensation of the newsulfonated aldehyde with dimethyl anilin, which will serve, bywayofexample,to illustrate the invention Twenty kilos ortho-sulfo-toluylicaldehyde, twentyfive kilos dimethylanilin, and three kilos concentratedsulfuric acid dissolved in one hundred and fifty liters of water isboiled for twelve to fifteen hours, the solution then diluted to fivethousand liters and oxidized with peroxid of lead or other suitableoxidizing agent. From the oxidized solution the lead is precipitatedwith sulfate of sodium filtered, the solution made alkaline with ammoniaand evaporated to dryness.

Instead of condensing one molecular proportion of ortho-sulfo-toluylicaldehyde with two molecular proportions of dimethyl-anilin I maysubstitute either two molecular proportions of another amin or itssulfo-acid or I may employ one molecular proportion of dimethyl-anilinor another aromatic amin and one molecular proportion of the sulfo-acidof an aromatic amin-as, for example,I may heat together twenty kilosortho-sulfo-toluylic aldehyde, twelve kilos dimethyl anilin, twentyeightkilos ethyl-benzyl-anilin sulfonic acid, three kilos concentratedsulfuric acid dissolved in one hundred and fifty liters water andproceed as above, or in place of dilute sulfuric acid I may employhydrochloric acid or zinc chlorid as condensing agent.

What I claim, and desire to secure by Letters Patent, is

1. The manufacture of a coloring-matter by condensingortho-sulfo-meta-toluylic aldehyde with an aromatic amin and oxidizingthe leuco product.

2. The manufacture of a coloring-matter by condensingortho-sulfo-meta-toluylic aldehyde with a substituted aromatic amin andoxidizing the leuco product.

The manufacture of a coloring-matter by condensingortho-sulfo-meta-toluylic aldehyde with an alkylated aromatic amin andoxidizing the leuco product.

4:. The manufacture of a coloring-matter by condensingortho-sulfo-meta-toluylic aldehyde with a dimethylated aromatic amin andoxidizing the leuco product.

5. The manufacture of a coloring-matter by condensingortho-sulfo-meta-tolnylic aldehyde with dimethyl anilin and oxidizingthe leuco product.

6. As a new product, a coloring-matter being the oxidized leucocondensation product of one molecule of ortho-sulfo-meta-toluylicaldehyde and two molecules of aromatic amin, and having the compositionO H (SO H)COH(X) where X indicates an aromatic amin radical, and whichcoloring-matter is soluble in water and dyes wool and silk bright-greento greenish-blue shades fast to alkalies.

7. As a new product, a coloring-matter being the oxidized leucocondensation product of one molecule of ortho-sulfo-meta-toluylicaldehyde and two molecules of a substituted aromatic amin, and havingthe composition C H (SO I-I) COH(X) wl1ere Xindicates a substitutedaromatic amin radical, and which coloring-matter is soluble in water anddyes wool and silk bright-green to greenish-blue shades fast toalkalies.

In witness whereof I have hereunto signed my name in the presence of twosubscribing witnesses.

JOSEPH KOETSOHET.

Witnesses:

WILHELM ROTH, MARIN VACHON.

